CN112920236B - Diterpene glycoside compound and preparation method and application thereof - Google Patents

Diterpene glycoside compound and preparation method and application thereof Download PDF

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CN112920236B
CN112920236B CN202110054654.2A CN202110054654A CN112920236B CN 112920236 B CN112920236 B CN 112920236B CN 202110054654 A CN202110054654 A CN 202110054654A CN 112920236 B CN112920236 B CN 112920236B
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晏霞
刘晶
欧阳翰
严小军
何山
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Ningbo University
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Abstract

The invention discloses diterpene glucoside compounds and a preparation method thereofAnd the application is characterized in that the diterpene glucoside compounds are prepared from marine soft coralLemnaliasp. secondary metabolite is separated, and the method comprises the following steps of 1) extracting frozen Borax glabra with acetone, then with ether and water, and concentrating the ether extract to obtain extract; 2) separating the crude extract with silica gel column chromatography, performing gradient elution with petroleum ether and ethyl acetate as mobile phase, collecting fraction, performing normal phase vacuum column chromatography, and purifying fraction No. 5 with mixed solution of acetonitrile and water as mobile phase with high performance liquid chromatography to obtain compounds 1-3; and (3) performing normal-phase medium-pressure column chromatography on the fraction No. 7, taking a mixed solution of petroleum ether and ethyl acetate as a mobile phase, collecting the fraction No. 14, and performing high performance liquid chromatography for purification to obtain a compound 4-6, wherein the compound has the advantage of moderately inhibiting the activity of the white blood cell CCRF-CEM cell line.

Description

Diterpene glycoside compound and preparation method and application thereof
Technical Field
The invention relates to the field of medicines, in particular to a Boraginacea schneiderianaLemnaliasp. separating the diterpene glucoside compound with bioactivity, and a preparation method and application thereof.
Background
In recent years, marine invertebrates have provided a large number of structurally diverse, biologically active secondary metabolites. Soft coralLemnaliasp. more than 30 species have been found, widely distributed in south China sea, Taiwan and Australia coast, etc. Up to now, about 15 kindsLemnaliaChemical studies of soft coral of genus have been isolated. By 2019, 102 terpenoids with different chemical structures have been obtainedLemnaliIsolated and identified in extracts, they exhibit a wide range of biological properties, including cytotoxic, antibacterial and anti-inflammatory activity.
The lenalifolins (lemnabourides) compound is a novel diterpene glycoside, originally produced by Zhang Min et al in 1994L. bourneiIs separated from the soft coral, and has the structural characteristic that D-type glucose is combined with diterpene aldehyde through an acetal bond. In 1998, Zhang Min et al isolated from this speciesTwo acetylated polaxanthosin named lemnabourside B and C have certain cytotoxicity. Then Amira Rudi et al were extracted from soft coralL. flavaFour new diterpene glycosides, namely lemnaflavoside and 3 acetylated diterpene glycosides, are separated from the extract. In subsequent studies, Guangmin Yao et al have sinceLemnaliaFour novel lemnalosides A-D were isolated in sp, showing moderate bacteriostatic activity against Streptomyces 85E.
Recently we have derived from the Ballon scale soft coral from the West Sha Jima of south China seaLemnaliasp. acetone extract to obtain 6 diterpene glycosides E-G and A-C. Wherein lemnabourside E is the 6' -O-acetate of lemnabourside, and lemnabourside F and G are the D-ring opened derivatives of lemnabourside acetate. Furthermore, lemnadiolbourides A-C have lemna-1(10) -ene-7, 12-diol as another aglycone of lemnabouride. At present, no report exists on the 6 structures and the activity of the 6 structures in inhibiting the white blood cell CCRF-CEM cell line.
Disclosure of Invention
The invention aims to provide a diterpene glucoside compound with moderate activity for inhibiting a white blood cell CCRF-CEM cell line, a preparation method and application thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: a diterpene glycoside compound is characterized in that the diterpene glycoside compound is prepared from marine soft coralLemnaliasp. and having a structural formula as shown in at least one of:
Figure 409599DEST_PATH_IMAGE001
。
the preparation method of the diterpene glucoside compound comprises the following steps:
(1) extracting the extractum: extracting frozen Bordetella fuliginosa with acetone, concentrating under reduced pressure to obtain extract, extracting the extract with mixed solution of equal volume of diethyl ether and water for 3 times, mixing diethyl ether extractive solutions, and concentrating under reduced pressure to obtain crude extract;
(2) dissolving the crude extract obtained in the step (1) by using a methanol solvent, performing normal-phase reduced pressure column chromatography, performing gradient elution by using a petroleum ether-ethyl acetate solution with a volume ratio of (100:1) - (1:1) as a mobile phase, collecting eluates tube by tube, arranging the eluates from small to large according to the polarity of the fractions, and combining to obtain 5 fractions;
(3) performing medium-pressure reverse phase column chromatography on the No. 3 fraction obtained in the step (2), performing gradient elution by using a methanol-water solution with the methanol content of 40wt% to 100wt% as a mobile phase, collecting eluates tube by tube, arranging the eluates from large to small according to the polarity of the fractions, and combining to obtain 9 fractions;
(4) performing high performance liquid chromatography separation on the No. 5 fraction obtained in the step (3), and performing isocratic elution by using an acetonitrile-water solution as a mobile phase to respectively obtain a compound lemnabourides E-G (1-3);
(5) performing normal-phase medium-pressure column chromatography on the No. 7 fraction obtained in the step (3), performing gradient elution by using petroleum ether-ethyl acetate solution with a volume ratio of (30: 1) - (5: 1) as a mobile phase, collecting eluate tube by tube, arranging the eluates from small to large according to fraction polarity, and combining to obtain 15 fractions;
(6) and (3) performing high performance liquid chromatography separation on the 14 th fraction obtained in the step (5), and performing isocratic elution by using an acetonitrile-water solution as a mobile phase to obtain a compound lemnadiolobasides A-C (4-6).
Preferably, the petroleum ether-ethyl acetate solution in the step (2) has an elution gradient volume ratio of 100: 1. 50: 1. 20: 1. 10: 1. 5: 1. 2: 1 and 1: 1.
preferably, the elution gradient of the methanol-water solution in the step (3) is 40%, 50%, 60%, 70%, 80%, 90% and 100% in sequence.
Preferably, the acetonitrile-water solution in the step (4) contains 80% of acetonitrile, the flow rate is 8mL/min, the isocratic time is 60min, the column temperature is room temperature, and the collection wavelength is 200 nm.
Preferably, the petroleum ether-ethyl acetate solution in the step (5) has an elution gradient volume ratio of 30: 1. 20: 1. 10: 1 and 5: 1.
preferably, the acetonitrile-water solution in the step (6) has an acetonitrile content of 99%, a flow rate of 8mL/min, an isocratic time of 60min, and a column temperature of room temperature.
The application of any one of the diterpene glucoside compounds 1-6 in preparing an inhibitor of leukemia cell CCRF-CEM cell line.
Compared with the prior art, the invention has the advantages that: the diterpene glycoside compounds provided by the invention have anti-tumor biological activity, can also be used as lead compounds, and lay a foundation for developing new drugs.
Drawings
FIG. 1 is a hydrogen nuclear magnetic resonance spectrum of the compound lemnabourside E;
FIG. 2 is a NMR carbon spectrum of the compound lemnabourside E;
FIG. 3 is a hydrogen nuclear magnetic resonance spectrum of the compound lemnabourside F;
FIG. 4 is a carbon NMR spectrum of the compound lemnabourside F;
FIG. 5 is a hydrogen nuclear magnetic resonance spectrum of the compound lemnabourside G;
FIG. 6 is a carbon NMR spectrum of the compound lemnabourside G;
FIG. 7 is a NMR spectrum of the compound lemnadiolobourside A;
FIG. 8 is a NMR carbon spectrum of the compound lemnadiolobourside A;
FIG. 9 is a hydrogen NMR spectrum of the compound lemnadiolobourside B;
FIG. 10 is a NMR carbon spectrum of the compound lemnadiolobourside B;
FIG. 11 is a hydrogen nuclear magnetic resonance spectrum of the compound lemnadiolobourside C;
FIG. 12 is a NMR carbon spectrum of the compound lemnadiolobourside C.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
Example 1
FromLemnaliaDiterpene glycoside compounds extracted and separated from coral softly: lemnabourides E-G (1-3) and lemnadiolobasides A-C (4-6), the chemical structures of which are shown below:
Figure 232061DEST_PATH_IMAGE002
。
example 2
The preparation method of the diterpene glucoside compound comprises the following specific steps:
1. extraction of secondary metabolites
Cutting frozen soft coral (wet weight 2.5 Kg) into small pieces, freeze-drying (dry weight 605 g), extracting with acetone under ultrasound for six times, concentrating under reduced pressure to obtain extract, extracting with mixed solution of equal volume of diethyl ether and water for three times, mixing diethyl ether extractive solutions, and concentrating under reduced pressure to obtain 60.3 g crude extract;
2. isolation preparation of compounds
(1) Dissolving the crude extract with a methanol solvent, performing normal-phase reduced pressure column chromatography, performing gradient elution by using petroleum ether-ethyl acetate solution with a volume ratio of (100:1) - (1:1) as a mobile phase, collecting eluates tube by tube, arranging the eluates from small to large according to fraction polarity, and combining to obtain 5 fractions (numbered from Fr.1 to Fr.5); wherein the elution gradient volume ratio of the petroleum ether-ethyl acetate solution is 100: 1. 50: 1. 20: 1. 10: 1. 5: 1. 2: 1 and 1: 1;
(2) performing medium-pressure reversed-phase column chromatography on the 3 rd fraction obtained in the step (1), performing gradient elution by using a methanol-water solution with the methanol content of 40-100 wt% as a mobile phase, collecting eluates tube by tube, arranging the eluates from large to small according to the polarity of the fractions, and combining to obtain 9 fractions (numbered Fr.3.1-3.9); wherein the elution gradient of the methanol-water solution is 40%, 50%, 60%, 70%, 80%, 90% and 100% (volume percentage of methanol) in this order;
(3) performing high performance liquid chromatography on the fraction No. 5 (Fr.3.5) collected in the step (2), and performing isocratic elution by using an acetonitrile-water solution as a mobile phase, wherein the acetonitrile content in the acetonitrile-water solution is 80%, the flow rate is 8mL/min, the isocratic time is 60min, the column temperature is room temperature, the collection wavelength is 200nm, so as to obtain a compound 1 (19.0 mg), a compound 2 (45.0 mg) and a compound 3 (33.0 mg), and the retention time is 46.0 min, 47.3 min and 50.3 min respectively;
(4) performing normal-phase medium-pressure column chromatographic separation on the No. 7 fraction (Fr.3.7) obtained in the step (2), performing gradient elution by using a petroleum ether-ethyl acetate solution with a volume ratio of (30: 1) - (1:1) as a mobile phase, collecting eluents tube by tube, arranging the eluents from small to large according to fraction polarities, and combining to obtain 15 fractions (Fr.3.7.1-3.7.15), wherein the elution gradient volume ratio of the petroleum ether-ethyl acetate solution is 30: 1. 20: 1. 10: 1 and 5: 1;
(5) and (3) performing high performance liquid chromatography separation on the No. 14 fraction (numbered 3.7.14) obtained in the step (4), performing isocratic elution by using an acetonitrile-water solution as a mobile phase, wherein the acetonitrile content in the acetonitrile-water solution is 99%, the flow rate is 8mL/min, the isocratic time is 60min, and the column temperature is room temperature to obtain a compound 4 (54.5 mg), a compound 5 (20.0 mg) and a compound 6 (32.0 mg), and the retention time is 41.3 min, 45.8 min and 50.4 min respectively, wherein the chemical structural formulas of diterpene glycoside compounds lemnabourides E-G (1-3) and lemnadiolubasides A-C (4-6) are as follows:
Figure 436778DEST_PATH_IMAGE002
。
example 3
Structural identification and nuclear magnetic signal assignment of compounds:
lemnabourside E (1): a white solid; [ alpha ] to]25 D﹢33（c 0.1，MeOH)；HRESIMS m/z 515.2977 [m + Na]+（calcd for C28H44O7Na, 515.2985) of this compound1H and13the C NMR data are shown in FIGS. 1 and 2, Table 1 and Table 2.
Lemnabourside F (2): a white solid; [ alpha ] to]25 D﹢20（c 0.1，MeOH)；HRESIMS m/z 559.3237 [M + Na]+ (calcd for C30H48O8Na, 559.3247) of this compound1H and13the C NMR data are shown in FIGS. 3 and 4, Table 1 and Table 2.
Lemnabourside G (3): a white solid; [ alpha ] to]25 D﹢13（c 0.1，MeOH)；HRESIMS m/z 601.3336 [M + Na]+ (calcd for C32H50O9Na, 601.3353) of this compound1H and13the C NMR data are shown in FIGS. 5 and 6, Table 1 and Table 2.
Lemnadiolbourside A (4): a white solid; [ alpha ] to]25 D﹢46（c 0.1，MeOH)；HRESIMS m/z 707.4481 [M + Na]+ (calcd for C41H64O8Na, 707.4499) of this compound1H and13the C NMR data are shown in FIGS. 7 and 8, Table 1 and Table 2.
Lemnadiolbourside B (5): a white solid; [ alpha ] to]25 D﹢76（c 0.1，MeOH)；HRESIMS m/z 707.4433 [M + Na]+ (calcd for C41H64O8Na, 707.4499) of this compound1H and13the C NMR data are shown in FIGS. 9 and 10, Table 1 and Table 2.
Lemnadiolbourside C (6): a white solid; [ alpha ] to]25 D﹢25（c 0.1，MeOH)；HRESIMS m/z 707.4433 [M + Na]+ (calcd for C41H64O8Na, 707.4499) of this compound1H and13the C NMR data are shown in FIGS. 11 and 12, Table 1 and Table 2.
Of Compounds 1 to 61H NMR data are shown in Table 1:
TABLE 1 preparation of Compounds 1 to 61H NMR(600MHz, CDCl3)
Figure 635678DEST_PATH_IMAGE003
Figure 304557DEST_PATH_IMAGE004
。
TABLE 2 preparation of Compounds 1 to 613C NMR(150MHz, CDCl3)
Figure 297920DEST_PATH_IMAGE005
Figure 989933DEST_PATH_IMAGE006
。
Example 4
The diterpene glycoside compounds 1-6 have inhibitory activity on leukemia cell CCRF-CEM cell line
1. Experimental sample
Preparing a solution of a sample to be detected: the test samples were pure compounds 1 to 6 isolated and purified in example 2, and an appropriate amount of the sample was precisely weighed and prepared into 50. mu.L of 20 mM stock solution with DMSO. The positive drug used in this experiment was cidalimine.
2. Experimental method
Counting the number of cells in the prepared cell suspension by using a cell counting plate, and then inoculating the cells into a culture plate; culturing for 2-4 hours after inoculation to make the cells adhere to the wall; 100 μ L of cell suspension was prepared in a 96-well plate. The plates were pre-incubated in an incubator for 24 hours (37 ℃ C., 5% CO)2) (ii) a Adding 10 mu L of substances to be detected with different concentrations into the culture plate; incubate the plates in the incubator for 48 hours; add 10. mu.L of CCK solution to each well; incubating the plate in an incubator for 1-4 hours; absorbance at 450 nm was measured with a microplate reader.
3. Results of the experiment
TABLE 3 anti-CCRF-CEM cell proliferation Activity of Compounds 1-6
Figure 726945DEST_PATH_IMAGE007
From the above table, it can be seen that compounds 1-6 have moderate inhibitory effect on CCRF-CEM leukemia cell line, IC50Is 10.4 to 21.0 mu M. The inhibition degree is not as good as that of a positive drug, but the compound can still be used as a lead compound for activity modification.
The above description is not intended to limit the present invention, and the present invention is not limited to the above examples. Those skilled in the art should also realize that changes, modifications, additions and substitutions can be made without departing from the true spirit and scope of the invention.

Claims (5)

1. A diterpene glycoside compound is characterized in that the diterpene glycoside compound is separated from a secondary metabolite of marine soft coral Lemna sp, and the structural formula of the diterpene glycoside compound is at least one of the following structures:
Figure FDA0003570061450000011
2. a method for preparing diterpene glycosides according to claim 1, characterized by comprising the steps of:
(1) extracting the extractum: extracting frozen Bordetella fuliginosa with acetone, concentrating under reduced pressure to obtain extract, extracting the extract with mixed solution of equal volume of diethyl ether and water for 3 times, mixing diethyl ether extractive solutions, and concentrating under reduced pressure to obtain crude extract;
(2) dissolving the crude extract obtained in the step (1) by using a methanol solvent, performing normal-phase reduced pressure column chromatography, performing gradient elution by using petroleum ether-ethyl acetate solution with a volume ratio of (100:1) to (1:1) as a mobile phase, collecting eluent tube by tube, arranging the eluents from small to large according to the polarity of the fractions, and combining to obtain 5 fractions;
(3) performing medium-pressure reversed-phase column chromatography on the No. 3 fraction obtained in the step (2), performing gradient elution by using a methanol-water solution with the methanol content of 40wt% to 100wt% as a mobile phase, collecting eluates tube by tube, arranging the eluates from large to small according to the polarity of the fractions, and combining to obtain 9 fractions;
(4) and (3) performing high performance liquid chromatography separation on the fraction No. 5 obtained in the step (3), and performing isocratic elution by using an acetonitrile-water solution as a mobile phase to obtain compounds 1-3 respectively, wherein the acetonitrile content in the acetonitrile-water solution is 80%, the flow rate is 8mL/min, the isocratic time is 60min, the column temperature is room temperature, and the collection wavelength is 200 nm.
3. The method for producing diterpene glycosides according to claim 2, characterized in that: the elution gradient volume ratio of the petroleum ether-ethyl acetate solution in the step (2) is 100: 1. 50: 1. 20: 1. 10: 1. 5: 1. 2: 1 and 1: 1.
4. the method for producing diterpene glycosides according to claim 2, characterized in that: the elution gradient of the methanol-water solution in the step (3) is 40%, 50%, 60%, 70%, 80%, 90% and 100% in sequence.
5. Use of any one of diterpene glycosides 1-3 of claim 1 for the preparation of an inhibitor of the leukemia cell CCRF-CEM cell line.
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